Fuel cell stack including witness marks and inspection method thereof

ABSTRACT

A fuel cell stack and inspection method, the fuel cell stack including fuel cells disposed in a stack and interconnects disposed between the fuel cells. Each fuel cell includes an electrolyte, an anode disposed on a first side of the electrolyte, a cathode disposed on an opposing second side of an electrolyte, and a witness mark disposed on the first side of the electrolyte. Each interconnect includes first ribs disposed on air side of the interconnect and at least partially defining oxidant channels, and second ribs disposed on an opposing fuel side of the interconnect and at least partially defining fuel channels. The witness mark of each fuel cell is visible from outside of the stack when the cathode directly faces the air side of an adjacent interconnect.

FIELD

The present invention is directed to fuel cells and inspection methods,specifically to fuel cell stacks including fuel cells having witnessmarks that are viewable outside of the stack.

BACKGROUND

A typical solid oxide fuel cell stack includes multiple fuel cellsseparated by metallic interconnects (IC) which provide both electricalconnection between adjacent cells in the stack and channels for deliveryand removal of fuel and oxidant.

SUMMARY

According to various embodiments, provided is a fuel cell stack andinspection method, the fuel cell stack including fuel cells disposed ina stack and interconnects disposed between the fuel cells. Each fuelcell includes an electrolyte, an anode disposed on a first side of theelectrolyte, a cathode disposed on an opposing second side of anelectrolyte, and a witness mark disposed on the first side of theelectrolyte. Each interconnect includes first ribs disposed on air sideof the interconnect and at least partially defining oxidant channels,and second ribs disposed on an opposing fuel side of the interconnectand at least partially defining fuel channels. The witness mark of eachfuel cell is visible from outside of the stack when the cathode directlyfaces the air side of an adjacent interconnect.

According to various embodiments, provided is a solid oxide fuel cellcomprising: a solid oxide electrolyte; a cathode disposed on a firstside of the electrolyte; an anode disposed on an opposing second side ofthe electrolyte; and a witness mark disposed on the electrolyte outsideof the perimeter of the cathode.

According to various embodiments, provided is a method of forming a fuelcell stack, the method comprising: assembling a fuel cell stackcomprising fuel cells having witness marks, and interconnects separatingthe fuel cells; externally inspecting the stack to identify any fuelcells that do not have witness marks that are visible outside of thestack; and determining whether any identified fuel cells are inverted ordefective.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a perspective view of a SOFC stack, according to variousembodiments of the present disclosure.

FIG. 1B is a cross-sectional view of a portion of the stack of FIG. 1A.

FIG. 2A is a plan view of an air side of an interconnect, according tovarious embodiments of the present disclosure.

FIG. 2B is a plan view of a fuel side of the interconnect of FIG. 2A.

FIG. 3A is a plan view of an air side of a fuel cell, according tovarious embodiments of the present disclosure.

FIG. 3B is a plan view of a fuel side of the fuel cell of FIG. 3A.

FIG. 4 is photograph of a fuel cell stack, according to variousembodiments of the present disclosure.

FIG. 5 is a block diagram of a method of forming a fuel cell stack,according to various embodiments of the present disclosure.

DETAILED DESCRIPTION

The various embodiments will be described in detail with reference tothe accompanying drawings. Wherever possible, the same reference numberswill be used throughout the drawings to refer to the same or like parts.References made to particular examples and implementations are forillustrative purposes, and are not intended to limit the scope of theinvention or the claims.

It will be understood that when an element or layer is referred to asbeing “on” or “connected to” another element or layer, it can bedirectly on or directly connected to the other element or layer, orintervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on” or “directly connected to”another element or layer, there are no intervening elements or layerspresent. It will be understood that for the purposes of this disclosure,“at least one of X, Y, and Z” can be construed as X only, Y only, Zonly, or any combination of two or more items X, Y, and Z (e.g., XYZ,XYY, YZ, ZZ).

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges is also encompassed within the invention, subject to anyspecifically excluded limit in the stated range. Where the stated rangeincludes one or both of the limits, ranges excluding either or both ofthose included limits are also included in the invention. It will alsobe understood that the term “about” may refer to a minor measurementerrors of, for example, 5 to 10%.

Words such as “thereafter,” “then,” “next,” etc. are not necessarilyintended to limit the order of the steps; these words may be used toguide the reader through the description of the methods. Further, anyreference to claim elements in the singular, for example, using thearticles “a,” “an” or “the” is not to be construed as limiting theelement to the singular.

The term “fuel cell stack,” as used herein, means a plurality of stackedfuel cells that can optionally share a common fuel inlet and exhaustpassages or risers. The “fuel cell stack,” as used herein, includes adistinct electrical entity which contains two end plates which areconnected directly to power conditioning equipment and the power (i.e.,electricity) output of the stack or comprises a portion of a fuel cellcolumn that contains terminal plates which provide electrical output.

Anode and cathode sides of fuel cells are difficult to distinguish. Assuch, during assembly of the stack, one or more fuel cells may beinadvertently inverted, such that an anode of the inverted fuel cellfaces the fuel side of an adjacent interconnect. During operation ofsuch a stack, the cathode of the inverted fuel cell is provided withfuel and an anode of the inverted fuel cell is provided with air,leading to the inactivation of the inverted fuel cell. Therefore,embodiments of the present disclosure provide a fuel cell stack andinspection method whereby improperly arranged fuel cells and/or fuelcells that lack a cathode or anode, may be easily identified fromoutside of the stack.

FIG. 1A is a perspective view of a fuel cell stack 100, and FIG. 1B is asectional view of a portion of the stack 100, according to variousembodiments of the present disclosure. Referring to FIGS. 1A and 1B, thestack 100 may be a solid oxide fuel cell (SOFC) stack that includes fuelcells 1 separated by interconnects 10. Referring to FIG. 1B, each fuelcell 1 comprises a cathode 3, a solid oxide electrolyte 5, and an anode7.

Various materials may be used for the cathode 3, electrolyte 5, andanode 7. For example, the anode 7 may comprise a cermet layer comprisinga nickel containing phase and a ceramic phase. The nickel containingphase may consist entirely of nickel in a reduced state. This phase mayform nickel oxide when it is in an oxidized state. Thus, the anode 7 ispreferably annealed in a reducing atmosphere prior to operation toreduce the nickel oxide to nickel. The nickel containing phase mayinclude other metals in additional to nickel and/or nickel alloys. Theceramic phase may comprise a stabilized zirconia, such as yttria and/orscandia stabilized zirconia and/or a doped ceria, such as gadolinia,yttria and/or samaria doped ceria.

The electrolyte 5 may comprise a stabilized zirconia, such as scandiastabilized zirconia (SSZ), scandia and ceria stabilized zirconia,scandia, ceria and ytterbia stabilized zirconia, or yttria stabilizedzirconia (YSZ). Alternatively, the electrolyte 5 may comprise anotherionically conductive material, such as a doped ceria.

The cathode 3 may comprise a layer of an electrically conductivematerial, such as an electrically conductive perovskite material, suchas lanthanum strontium manganite (LSM). Other conductive perovskites,such as LSCo, etc., or metals, such as Pt, may also be used. The cathode3 may also contain a ceramic phase similar to the anode 7. Theelectrodes and the electrolyte may each comprise one or more sublayersof one or more of the above described materials.

Fuel cell stacks are frequently built from a multiplicity of fuel cells1 in the form of planar elements, tubes, or other geometries. Althoughthe fuel cell stack 100 in FIG. 1 is vertically oriented, fuel cellstacks may be oriented horizontally or in any other direction. Fuel andair may be provided to the electrochemically active surface, which canbe large. For example, fuel may be provided through fuel conduits 22(e.g., fuel riser openings) formed in each interconnect 10 and fuel cell1, while air may be provided from the side of the stack between air sideribs of the interconnects 10.

Each interconnect 10 electrically connects adjacent fuel cells 1 in thestack 100. In particular, an interconnect 10 may electrically connectthe anode 7 of one fuel cell 1 to the cathode 3 of an adjacent fuel cell1. FIG. 1B shows that the lower fuel cell 1 is located between twointerconnects 10. A Ni mesh (not shown) may be used to electricallyconnect the interconnect 10 to the anode 7 of an adjacent fuel cell 1.

Each interconnect 10 includes fuel-side ribs 12A that at least partiallydefine fuel channels 8A and air-side ribs 12B that at least partiallydefine oxidant (e.g., air) channels 8B. The interconnect 10 may operateas a gas-fuel separator that separates a fuel, such as a hydrocarbonfuel, flowing to the fuel electrode (i.e. anode 7) of one cell in thestack from oxidant, such as air, flowing to the air electrode (i.e.cathode 3) of an adjacent cell in the stack. At either end of the stack100, there may be an air end plate or fuel end plate (not shown) forproviding air or fuel, respectively, to the end electrode.

Each interconnect 10 may be made of or may contain electricallyconductive material, such as a metal alloy (e.g., chromium-iron alloy)which has a similar coefficient of thermal expansion to that of thesolid oxide electrolyte in the cells (e.g., a difference of 0-10%). Forexample, the interconnects 10 may comprise a metal (e.g., achromium-iron alloy, such as 4-6 weight percent iron, optionally 1 orless weight percent yttrium and balance chromium alloy), and mayelectrically connect the anode or fuel-side of one fuel cell 1 to thecathode or air-side of an adjacent fuel cell 1. An electricallyconductive contact layer, such as a nickel contact layer, may beprovided between anodes 7 and each interconnect 10. Another optionalelectrically conductive contact layer may be provided between thecathodes 3 and each interconnect 10.

FIG. 2A is a top view of the air side of the interconnect 10, and FIG.2B is a top view of a fuel side of the interconnect 10, according tovarious embodiments of the present disclosure. Referring to FIGS. 1B and2A, the air side includes the air channels 8B that extend from opposingfirst and second edges 30, 32 of the interconnect 10. Air flows throughthe air channels 8B to a cathode 3 of an adjacent fuel cell 1. Ringseals 20 may surround fuel holes 22A of the interconnect 10, to preventfuel from contacting the cathode. Strip-shaped peripheral seals 24 arelocated on peripheral portions of the air side of the interconnect 10.The seals 20, 24 may be formed of a glass or glass-ceramic material. Theperipheral portions may be an elevated plateau which does not includeribs or channels. The surface of the peripheral regions may be coplanarwith tops of the ribs 12B.

In some embodiments, the air side of the interconnect 10 may include awindow region 40. The window region 40 may be disposed on the first edge30 and/or the second edge 32 of the interconnect 10, between one of thering seals 20 and one of the peripheral seals 24. Accordingly, thewindow region 40 may extend from an edge of the interconnect 10, in anarea that is not covered by the seals 20, 24. In other words, the windowregion 40 and the seals 20, 24 do not overlap.

The width of the window region 40, taken in a direction perpendicular tothe air channels 8B, may range from about 0.25 cm to about 1.5 cm, suchas from about 0.5 cm to about 1 cm, or about 0.75 cm. The length of thewindow region 40, taken in a direction parallel to the air channels 8B,may range from about 0.5 cm to about 2.0 cm, such as from about 0.75 cmto about 1.5 cm, or about 1.0 cm.

Within the window region 40, the ribs 12B may be reduced in height byfrom about 25% to about 95%, such as by from about 50% to about 90%, orby about 75%, as compared to the height of the reminder of the ribs 12B.In other embodiments, the ribs 12B may be absent or removed from thewindow region 40. In further embodiments, the window region 40 may befree of the ribs 12B and the thickness of the corresponding portion ofthe interconnect 10 may be reduced.

Referring to FIGS. 1B and 2B, the fuel side of the interconnect 10 mayinclude the fuel channels 8A and fuel manifolds 28. Fuel flows from oneof the fuel holes 22A (e.g., inlet fuel hole that forms part of the fuelinlet riser), into the adjacent manifold 28, through the fuel channels8A, and to an anode 7 of an adjacent fuel cell 1. Excess fuel may flowinto the other fuel manifold 28 and then into the outlet fuel hole 22B.A frame seal 26 is disposed on a peripheral region of the fuel side ofthe interconnect 10. The peripheral region may be an elevated plateauwhich does not include ribs or channels. The surface of the peripheralregion may be coplanar with tops of the ribs 12A.

FIG. 3A is a plan view of a cathode side (e.g., air side) of the fuelcell 1, and FIG. 3B is a plan view of an anode side (e.g., fuel side) ofthe fuel cell 1, according to various embodiments of the presentdisclosure. Referring to FIGS. 1A, 2A, 3A, and 3B, the fuel cell 1 mayinclude an inlet fuel hole 22A, an outlet fuel hole 22B, the electrolyte5, and the cathode 3. The cathode 3 may be disposed on a first side ofthe electrolyte 5. The anode 7 may be disposed on an opposing secondside of the electrolyte 5. The fuel cell 1 may include a first edge 30and an opposing second edge 32 that correspond to the first and secondedges 30, 32 of the interconnect 10.

The fuel holes 22A, 22B may extend through the electrolyte 5 and may bearranged to overlap with the fuel holes 22A, 22B of the interconnects10, when assembled in the fuel cell stack 100. The cathode 3 may beprinted on the electrolyte 5 so as not to overlap with the ring seals 20and the peripheral seals 24 when assembled in the fuel cell stack 100.The anode 7 may have a similar shape as the cathode 3. The anode 7 maybe disposed so as not to overlap with the frame seal 26, when assembledin the stack 100. In other words, the cathode 3 and the anode 7 may berecessed from the edges of the electrolyte 5, such that correspondingedge regions of the electrolyte 5 may directly contact the correspondingseals 20, 24, 26.

The fuel cell 1 includes at least one witness mark 50 on at least oneside of the fuel cell 1, such as on the cathode side. The witness mark50 may be disposed so as to overlap with the window region 40 of anadjacent interconnect 10, when assembled in the fuel cell stack 100. Forexample, the witness mark 50 may be disposed on the first edge 30 of thefuel cell 1. However, in other embodiments, the witness mark 50 may bedisposed on the second edge 32 of the fuel cell 1, or on both the firstand second edges 30, 32 of the fuel cell 1. Alternatively, multiplewitness marks 50 may be disposed on one edge or on plural edges of thefuel cell 1 for visual confirmation from all sides of the stack, as wellas for further verification. For example, as shown in FIG. 3A, one ormore first witness marks 50 (e.g., three witness marks) may be disposedon the first edge 30 of the fuel cell 1, and one or more second witnessmarks 50 (e.g., three witness marks) may be disposed on the second edge32 of the fuel cell 1. In the embodiment shown in FIG. 3A, the witnessmarks are provided on the same location (e.g., same corner) even if thestack or the fuel cell 1 is rotated at 180°.

Accordingly, the witness mark 50 extends from one or more edges of thefuel cell 1, in one or more areas that do not overlap with the seals 20,24. In other words, the witness mark 50 and the seals 20, 24 do notoverlap in the stack 100. Alternatively, the witness mark 50 may beslightly offset from the edge(s) of the fuel cell 1 and may be locatedbetween the cathode 3 and the edge(s) (30, 32) of the electrolyte 5.

The witness mark 50 may have similar dimensions to the window region 40.For example, the width of the witness mark 50, taken in a directionperpendicular to the air channels 8B, may range from about 0.25 cm toabout 1.5 cm, such as from about 0.5 cm to about 1 cm, or about 0.75 cm.The length of the witness mark 50, taken in a direction parallel to theair channels 8B, may range from about 0.5 cm to about 2.0 cm, such asfrom about 0.75 cm to about 1.5 cm, or about 1.0 cm. However, in someembodiments, the witness mark 50 may be larger or smaller than thewindow region 40.

The witness mark 50 may be printed on the electrolyte 5 using an inkthat is stable at fuel cell operating temperatures, such as temperaturesof 600° C. or higher. Accordingly, the witness mark 50 may be visibleafter sintering the fuel cell stack 100. In some embodiments, thewitness mark 50 and the cathode 3 may be formed using the same ink(e.g., LSM ink) or different inks. The witness mark 50 may have anycolor, so long as the witness mark 50 is easily distinguishable from theelectrolyte 5 by visual or optical inspection.

In some embodiments, the witness mark 50 may be at least one tab,cutout, or groove formed on the electrolyte 5, such as in the edge (30,32) of the electrolyte 5, and/or in a region of the electrolyte 5between the edge (30, 32) of the electrolyte 5 and the cathode 3.Accordingly, the witness mark 50 may be any type of mark that may beused to optically identify a particular side of the fuel cell 1.

In another embodiment, the witness mark 50 is printed on the cathodeside of the electrolyte 5 at the same time as when the cathode 3 isprinted to indicate the presence of the cathode 3. In addition or in thealternative, the witness mark 50 may be printed on the anode side of theelectrolyte 5 at the same time as the anode 7 to indicate the presenceof the anode 7.

FIG. 4 is a photograph of a portion of a fuel cell stack 101, accordingto various embodiments of the present disclosure. The stack 101 issimilar to the stack 100 of FIG. 1, where like reference numbers referto like elements.

Referring to FIG. 4, the fuel cell stack 101 includes interconnects 10that include window regions 40, which are stacked between adjacent fuelcells 1 that include witness marks 50. As can be seen in FIG. 4, thewindow regions 40 overlap and expose the witness marks 50, such that thewitness marks 50 may be easily identified from outside of the fuel cellstack 101. Since the witness marks 50 are disposed on the cathode sideof each fuel cell 1, visible witness marks 50 can be used to identifythe cells 1 that are properly oriented in the fuel cell stack 101.Similarly, the lack of a visible witness mark 50 can be used to identifycells that are not properly aligned (e.g., that are inverted with thecathode 3 facing the fuel channels of an adjacent interconnect) or toidentify fuel cells that lack an anode or cathode.

For example, as shown in FIG. 4, fuel cell 1A is inverted with respectto the fuel cells 1. In other words, the cathode of the fuel cell 1Acontacts the fuel side of an adjacent interconnect 10. As a result, thewitness mark of the fuel cell 1A faces downward and is covered by aframe seal of the stack 101 and thus, is not visible withoutdisassembling the stack 101. Further, only an unmarked portion of theelectrolyte of the cell 1A is visible through the adjacent window region40. As such, a technician or an automated optical device can readilydetermine that fuel cell 1A is not properly oriented, through anexternal inspection the stack 101. For example, an automated opticalinspection apparatus to detect the witness marks using infraredradiation or visible light that is provided onto the witness marks 50.

Accordingly, witness marks may be used, with or without correspondingwindow regions, to easily identify improperly oriented/inverted fuelcells and/or fuel cells lacking a cathode or anode, in a fuel cellstack.

FIG. 5 is a block diagram depicting a method of forming a fuel cellstack, according to various embodiments of the present disclosure.Referring to FIG. 5, in step 500, the method includes assembling a fuelcell stack. For example, the fuel cell stack may include fuel cellshaving witness marks and interconnects that may optionally includewindow regions. In some embodiments, step 500 may optionally includeforming witness marks on fuel cells, as described above. The stack isassembled by alternately stacking fuel cells and interconnects with sealmaterial located between them.

In step 502, the method includes inspecting the fuel cell stack. Forexample, the inspection may include a visual inspection by a person(e.g., technician) or an optical inspection using an automatedinspection apparatus.

In step 504, a determination is made as to whether any fuel cells do nothave visible witness marks when inspected from the side of the stack areidentified. If any such fuel cells are identified, the method proceedsto step 506. In one embodiment, when the first fuel cell without avisible witness mark is identified, then the method proceeds to step506. In another embodiment, the entire stack is inspected, and thelocation of all identified fuel cells lacking the visible witness markis noted. The method then proceeds to step 506 after the entire stack isinspected.

In step 506, a determination is made as to whether the identified fuelcell is inverted or is a defective fuel cell (e.g., lacks an anode orcathode). If step 504 proceeds to step 506 after identification of thefirst fuel cell that lacks a witness mark, then the determination instep 506 is made on only the single identified fuel cell. If step 504includes inspection of the entire stack, then the determination in step506 is made on all identified fuel cells in the stack. The inspectionmay be visual or may utilize an automated inspection apparatus.

If an identified fuel cell or cells is/are inverted, then in step 508,the stack is partially disassembled and the identified fuel cell may berepositioned to obtain the proper orientation. For example, theidentified fuel cell may be flipped upside down in the stack, and therest of the stack elements placed back in the stack in the originalorder. If step 504 proceeds to step 506 after identification of thefirst fuel cell that lacks a witness mark, then the method may thenreturn to step 500. If step 504 includes inspection of the entire stack,then the method may be completed at step 512 after repositioning and/orreplacement of all identified fuel cells in the stack.

If an identified fuel cell is determined to be defective (e.g., lackingone or both electrodes) in step 506, then the method proceeds to step510 and the defective fuel cell may be removed from the stack andreplaced with a non-defective fuel cell that includes both electrodes.If step 504 proceeds to step 506 after identification of the first fuelcell that lacks a witness mark, then the method may then return to step500. If step 504 includes inspection of the entire stack, then themethod may be completed at step 512 after repositioning and/orreplacement of all identified fuel cells in the stack.

If the identified fuel cell is determined to be neither inverted nordefective after inspection (e.g., if the identified fuel cell has amissing witness mark or an improperly placed witness mark), then themethod either returns to step 502 or ends at step 512.

Once the entire stack has been inspected and it is determined that allfuel cells in the stack have witness marks, the method ends at step 512.

Although the foregoing refers to particular preferred embodiments, itwill be understood that the invention is not so limited. It will occurto those of ordinary skill in the art that various modifications may bemade to the disclosed embodiments and that such modifications areintended to be within the scope of the invention. All of thepublications, patent applications and patents cited herein areincorporated herein by reference in their entirety.

What is claimed is:
 1. A solid oxide fuel cell comprising: a solid oxideelectrolyte; a cathode disposed on a first side of the electrolyte; ananode disposed on an opposing second side of the electrolyte; and awitness mark disposed on the electrolyte outside of a perimeter of thecathode.
 2. The solid oxide fuel cell of claim 1, wherein the witnessmark is disposed on an edge of the electrolyte and is not covered by thecathode.
 3. The solid oxide fuel cell of claim 1, wherein: the witnessmark is formed by depositing an ink that is stable at a temperature ofat least 600° C.; and the witness mark has a first color and theelectrolyte has a different second color.
 4. The stack of claim 1,wherein the witness mark comprises at least one notch or cutout formedin an edge the electrolyte.
 5. A method of forming a fuel cell stack,the method comprising: assembling a fuel cell stack comprising fuelcells having witness marks, and interconnects separating the fuel cells;externally inspecting the stack to identify any fuel cells that do nothave witness marks that are visible outside of the stack; anddetermining whether any identified fuel cells are inverted or defective.6. The method of claim 5, wherein when any identified fuel cell isdetermined to be inverted, the method further comprises: at leastpartially disassembling the stack; and repositioning the inverted fuelcell and reassembling the stack, such that the witness marks of therepositioned fuel cell is visible outside of the stack.
 7. The method ofclaim 6, wherein the repositioning the inverted fuel cell comprisesinverting the inverted fuel cell.
 8. The method of claim 5, wherein whenany of the identified fuel cell is determined to be defective due tolack of at least one of the anode or the cathode, the method furthercomprises: at least partially disassembling the stack; and replacing thedefective fuel cell with a non-defective fuel cell that includes theanode and the cathode.
 9. The method of claim 5, wherein: theinterconnects comprise window regions configured to increase thevisibility of the witness marks; the interconnects comprise ribsdisposed on air side of each interconnect and at least partiallydefining oxidant channels; the ribs have a reduced height in the windowregions as compared to a remainder of the ribs or the ribs are notpresent in the window regions; and assembling the fuel cell stackcomprises overlapping the witness marks and the window regions in astacking direction of the fuel cells.
 10. The method of claim 5, whereinexternally inspecting the stack comprises: visually inspecting thestack; or using an automated device to optically inspect the stack.